The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

Coulometric total carbon dioxide analysis for marine studies: maximizing the performance of an automated gas extraction system and coulometric detector

A global survey of the distribution of dissolved CO₂ taking advantage of sampling opportunities provided by the World Ocean Circulation Experiment: World Hydrographic Program (WOCE-WHP) is being carried out through 1995. Goals include the measurement of oceanic inorganic carbon transport and the development of a data base from which future fossil-fuel CO₂ build-up can be monitored. The analytical method selected for total carbon dioxide (C_T) is gas extraction of acidified seawater with coulometric titration of the acid formed by the resultant carbon dioxide and monoethanolamine. To combine high accuracy and precision (± 1.5 μmol/kg for C_T ≥ 2000 μmol/kg) with a high rate of analysis, we have modified an automated single-parameter system. Following prototype development between 1987 and 1990, an instrument emerged with the acronym Somma standing for single-operator multiparameter metabolic analyzer. Improved functional and operating procedures have integrated electronic calibration, CO₂ gas calibration, and sample analysis with automated pressure, temperature, and conductivity (salinity) sensing into a single convenient transportable package.     

JGOFS studies in the equatorial Pacific

This special issue is the third and final volume containing results from the JGOFS Process Study in the equatorial Pacific. Most of the Study in the equational Pacific. Most of the contributions evolved either from the US JGOFS workshop in 1994 on the equatorial Pacific in Scottsdale, AZ or from the NATO Advanced Research Workshop on the Carbon Cycle of the Equatorial Pacific in 1995 in Noumea, New Caledonia.     

Variability in concentration of suspensates in an estuarine environment

Three data sets of suspensate concentrations, collected under different sampling plans, were analyzed to develop a minimal sampling period, consistent with a predetermined precision. Individual samples collected during any part of a given day were within ±50% of the daily average. In the main channel of the estuary, a monthly sampling scheme closely approximated a weekly pattern; however, seasonal sampling was unsatisfactory. Outside the main channel, weekly, monthly, and seasonal sampling patterns did not differ greatly. Variability in suspensate concentrations must be considered when calculating sediment flux in estuarine and coastal waters.     

Accumulation of organic and inorganic carbon in Pliocene–Pleistocene sediments along the SW African margin

The Ocean Drilling Program Leg 175 recovered a unique series of stratigraphically continuous sedimentary sections along the SW African margin, an area which is presently affected by active coastal upwelling. The accumulation rates of organic and inorganic carbon are a major component of this record. Four Leg 175 sites (1082, 1084, 1085, 1087) are chosen as part of a latitudinal transect from the present northern to southern boundaries of the Benguela Current upwelling system, to decipher the Pliocene–Pleistocene history of biogenic production and its relationship with global and local changes in oceanic circulation and climate. The pattern of CaCO₃ and C_org mass accumulation rates (MARs) over 0.25-Myr intervals indicates that the evolution of carbon burial is highly variable between the northern and the southern Benguela regions, as well as between sites that have similar hydrological conditions. This, as well as the presence over most locations of high-amplitude, rapid changes of carbon burial, reflect the partitioning of biogenic production and patterns of sedimentation into local compartments over the Benguela margin. The combined mapping of CaCO₃ and C_org MARs at the study locations suggests four distinct evolutionary periods, which are essentially linked with major steps in global climate change: the early Pliocene, the mid-Pliocene warm event, a late Pliocene intensification of northern hemisphere glaciation and the Pleistocene. The early Pliocene spatially heterogeneous patterns of carbon burial are thought to reflect the occurrence of mass-gravitational movements over the Benguela slope which resulted in disruption of the recorded biogenic production. This was followed (3.5–3 Ma) by an episode of peak carbonate accumulation over the whole margin and, subsequently, by the onset of Benguela provincialism into a northern and a southern sedimentary regime near 2 Ma. This mid and late Pliocene evolution is interpreted as a direct response to changes in the ventilation of bottom and intermediate waters, as well as to dynamics of the subtropical gyral circulation and associated wind stress.     

Diel fluctuations in dissolved free amino acids and monosaccharides in Chesapeake Bay dinoflagellate blooms

The accumulation of phytoplankton biomass in recurring summer dinoflagellate blooms of Chesapeake Bay is accompanied by large pools of dissolved organic matter (DOM). Two fractions of the DOM, free amino acids (DFAA) and monosaccharides (MONO), were measured at 3 h intervals in mixed species dinoflagellate blooms (Katodinium rotundatum, Gymnodinium spp.) and related to productivity, biomass and photoperiod. Peak chlorophyll levels for the three blooms were 28, 65 and 938 μg1⁻¹. In general, DFAA and MONO concentrations increased with increasing biomass of bloom-forming species, reaching 203 and 844 μg1⁻¹. MONO appeared to accumulate during the day while there was no consistent pattern for DFAA. The accumulations of DFAA and MONO in blooms indicate that bloom production might stimulate microheterotrophy, thereby enhancing carbon and nutrient cycling in bloom-impacted regions.